Highly-ordered microporous carbon (MPC) nanospheres were prepared by a simple hydrothermal route based on a soft template. The interlayer spacing of the MPC was well tuned by simply adjusting the heat-treatment temperatures. The as-obtained carbon spheres treated at 700 °C (MPC-700) combine the features required for high-performance sodium-ion battery (SIB) electrode materials, such as a large interlayer spacing (∼0.457 nm), high surface area, structural stability and plenty of micropores for Na insertion, which synergistically contribute to their impressive electrochemical properties. When applied as an anode for SIBs, the MPC-700 electrode exhibits a high reversible capacity, good cycling stability, and an excellent high-rate performance (∼160 mA h g⁻¹ after 500 cycles at 1000 mA g⁻¹), making it a promising candidate for SIB anodes.